三噻吩的合成及其应用

三噻吩是极其重要的有机合成中间体，而且其衍生物结构新颖，具有独特的活性，在许多领域有重要用途，品种和数量正快速增长。目前，三噻吩的合成主要是采用格氏Grignard反应制得的，有待于研究比较温和的反应条件。本文综述了国内外三噻吩的合成及在光电材料、液晶材料、农药上的应用，最后对三噻吩及其衍生物的合成应用前景加以展望。     

3-巯基噻吩化学研究进展

较为详细的对3-巯基噻吩的制备方法进行了综述.同时介绍了3-巯基噻吩发生的一些典型反应,重点介绍3-噻吩硫基化合物分子内环合生成噻吩并含硫杂环化合物这一类反应.最后展望了3-巯基噻吩及其衍生物在医药化工及食品化学方面的一些应用前景.     

噻吩甲醛的生产与应用

介绍了在三氯氧磷存在下,噻吩与N,N-二甲基甲酰胺缩合后,经水解、中和、精制制备 噻吩甲醛的合成方法及生产现状。着重介绍了在替尼酮、噻嘧啶、替尼泊苷等药物合成及噻吩乙胺 等中间体合成方面的应用,并就噻吩甲醛的生产应用及市场开拓提出了一些建议。     

噻吩及其在医药中间体合成中的应用

综述了近年来国内外噻吩生产方法的研究进展。介绍了噻吩在噻吩甲醛、2-噻吩乙酸、2-（2-噻吩基）丙酸、2-噻吩乙醇、2-噻盼乙胺、3-巯基噻吩等医药中间体合成中的应用现状。并对噻吩及其下游产品的进一步研究和应用进行了展望。     

2-噻吩甲胺类化合物的合成及其应用研究

2-噻吩甲胺是一种重要的药物中间体,由于它及其衍生物具有独特的化学反应活性及生物活性,已被越来越多的研究者所重视。本文对2-噻吩甲胺类化合物合成进展及其典型应用进行了综述,并对各种制备方法进行了分析和概括,为探索一条合理的2-噻吩甲胺制备工艺路线提供相应的参考。     

噻吩乙胺的合成及其在药物中的应用

介绍了重要医药中间体噻吩乙胺的合成方法及生产现状，及其在药物合成中的应用前景。     

噻吩及其同系物生产与应用

噻吩类化合物是一种新型极具发展潜力的系列精细化学品。我国由于原料资源、技术、市场等问题一直影响其发展。本作着重介绍了噻吩及其同系物的特点、生产技术、开发及应用，并建议有条件的企业应与科研单位联系，开发下游深加工产品，做到精细化、系列化和高附加值化。     

2-噻吩乙胺的研究进展

综述了2-噻吩乙胺的结构及制备方法,介绍了2-噻吩乙胺国内外发展现状及其应用,并提出了目前的主要研究趋势.     

2-噻吩乙醇的合成技术及其在药物中的应用

介绍了重要医药中间体2-噻吩乙醇的合成方法,主要有丁基锂工艺、格氏试剂工艺、钠试剂工艺和酯还原工艺,其中,前三种路线都是以噻吩为原料,经不同的步骤得到噻吩的金属化合物,最后与环氧乙烷反应,水解得2-噻吩乙醇,酯还原工艺是以噻吩乙酸酯为原料,在催化剂作用下,将酯还原为伯醇.总结了各方法的进展状况和优缺点,并对2-噻吩乙醇在噻吩并吡啶类药物特别是盐酸噻氯匹啶和氯吡格雷中的应用及前景作了简要概述.     

可溶性导电高分子的合成与研究

研究了导电高分子聚－３－庚基噻吩及单体３－庚基噻吩的合成，对高分子性能进行测试和分析。     

Kinetics and Mechanism of Liquid-Phase Oxidation of Thiophene over TS-1 Using H2O2 Under Mild Conditions

Thiophene is a typical thiophenic sulfur compound in gasoline. Using n-octane containing thiophene as the model compound, the oxidation of thiophene, which is a key step for the oxidative deep desulfurization of gasoline, was carried out to study the reactivity of thiophene in oxidation reactions. It has been observed that thiophene oxidation can occur using water or t-butanol as solvent. Kinetics of the reaction shows a pseudo-first-order toward thiophene or catalyst and a zero order toward hydrogen peroxide. The mechanism for this unique reaction was proposed as the activation of conjugated electron in thiophene ring.     

用氯甲基化脱除焦化苯中噻吩的研究

研究了用氯甲基化脱除焦化苯及轻苯中噻吩的方法,通过对噻吩基化反应的温度与原料配比的考察表明,焦化苯中的噻吩可完全转化为噻吩聚合物,在反应温度为70℃,焦化苯（含噻吩1.4g/L),甲醛：HCl=6:1:1条件下,搅拌反应3h,苯中的噻吩肿除率可达100％。     

Untersuchungen zur Sorption von Thiophen aus dem Lösungsmittel mittels eines Ni-Katalysators in stationärer Anordnung

Investigations about Sorption of Thiophene from the Solvent by Means of a Ni-Catalyst in Stationary Arrangement In the work the dependence of the adsorption of sulfur by Ni-catalyst on the concentration of thiophene, solved in isopropanol, under normal pressure and temperature is investigated. The degree of adsorption of the tabletted Ni-catalyst was in the range of 70% for low thiophene concentrations (0.0166 mg thiophene/g Ni) upto 47% for a concentration of 3.38 mg thiophene/g Ni. It was found that the dependence of the equilibrium concentration of the sulfur, which is to be sorbed, is linear to the added amount of thiophene. 9.3 mg S/g Ni of the added thiophene were adsorbed by pulverized Ni-catalyst. The active surface of the Ni-catalyst was detected from the degree of adsorption of the thiophene. It was 57.7 m²/g Ni, if the catalyst was pulverized and 0.65 to 29.8 m²/g Ni if the catalyst was tabletted according to the degree of adsorption of the thiophene in the pores of the catalyst and the poison concentration.     

Studies on 3‐(2‐Ethylhexyl)thiophene Polymers

The regio‐regularity and properties of the poly[3‐(2‐ethylhexyl)thiophene] were studied, and compared with the poly[3′‐(2‐ethylhexyl)‐2,2′,5′,2′′‐terthiophene]. The thermal stability of the polymers was improved due to the addition of thiophene rings with (2‐ethylhexyl)thiophene. Due to the additional thiophenes at the 2,5 position of ethylhexylthiophene, even though the absorption wavelength was red‐shifted, there is no characteristic change in photoemission for the latter polymer. Addition of thiophene rings to the 3‐(2‐ethylhexyl)thiophene improves the thermal properties without loosing the 3‐(2‐ethylhexyl)thiophene characteristics.     

Preparation of polypyrrole/polythiophene double layers by electrochemical polymerization of pyrrole in the presence of thiophene

Studies on electrochemical polymerization of pyrrole in the presence of thiophene are given for preparation of polypyrrole (PPy)/polythiophene (PTh) double layers. At a constant current, only pyrrole is electrochemically polymerized in the electrolytic solution containing pyrrole and thiophene in the present experiments. The cyclic voltammograms on pyrrole/thiophene mixtures are similar to that on pyrrole. Preparation of PPy/PTh double layers is carried out by electrochemical polymerization of pyrrole in the presence of thiophene by adding pyrrole and by lowering voltage immediately after electrochemical homopolymerization of thiophene. The resulting double layers show good rectification characters dependent on thickness. © 1995 John Wiley & Sons, Inc.     

FCC gasoline desulfurization using a ZSM-5 catalyst: Interactive effects of sulfur containing species and gasoline components

This study evaluates the influence of gasoline hydrocarbon components on thiophene conversion over H-ZSM5 zeolite. Experiments are carried out in a CREC fluidized riser simulator under mild conditions using thiophene/hydrocarbon mixtures as representatives of gasoline. Results show a high and selective thiophene conversion, forming H₂S, aromatics, alkyl-thiophenes, benzothiophene, and coke. It is also found that gasoline octane number is enhanced and olefin content reduced. This is accomplished with minimum gasoline losses. On the basis of the data reported it is hypothesized that thiophene conversion takes place via ring opening and alkylation, with gasoline hydrocarbon components having key roles as hydrogen donors in thiophene ring opening reactions as well as co-reactants in thiophene alkylation. These observations are in good agreement with previous thermodynamic and kinetic analysis developed using sulfur containing compounds by the CREC-UWO research group [4] and [10].     

采用反应-精馏法对焦化纯苯进行脱硫精制的研究

采用反应-精馏法对焦化纯苯中噻吩进行脱除,探讨了硫酸用量、填料层高度、填料种类及回流情况等主要影响因素对噻吩脱除率的影响。结果表明,对400mL噻吩质量浓度为0.030g/100mL的噻吩-苯溶液,采用玻璃多圈柱状填料,填料层高度为40cm,硫酸用量为80mL,人工控制回流情况,噻吩脱除率可达94%以上,苯中噻吩的质量分数小于2×10-5。     

Cu~+-13X上噻吩与苯并噻吩的竞争吸附

以噻吩(TP)、苯并噻吩(BT)和正己烷配制模拟汽油,就如何提高Cu+-13X分子筛对噻吩的选择性进行了一系列的静态吸附及动力学吸附研究。结果表明:增加模拟汽油中噻吩的初始质量分数,可以增大Cu+-13X对噻吩的吸附量,提高噻吩对苯并噻吩的竞争吸附性能。当模拟汽油中苯并噻吩、噻吩的初始质量分数分别为500,700μg/g时,Cu+-13X对噻吩的吸附量就大于苯并噻吩;当模拟汽油中苯并噻吩、噻吩的初始质量分数分别为350,850μg/g时,Cu+-13X对噻吩的选择性大于苯并噻吩,噻吩在竞争吸附中占优势。     

Y型沸石吸附噻吩的能量及结构异质性的分子模拟

采用GCMC方法计算了噻吩在全硅Y和NaY沸石上的吸附,通过变化不同的噻吩吸附量得到吸附能量的异质性,并基于主客体径向分布函数剖析了吸附能量的异质性。根据对噻吩分子与沸石之间能量的分析,噻吩分子与沸石之间的作用主要由短程的色散作用控制。NaY沸石上吸附表现出与全硅Y沸石明显不同的吸附位特征,钠离子的引入明显地增强了对噻吩的吸附作用。钠离子与噻吩之间的静电和色散作用是引起这两种不同化学组成沸石吸附热不同的重要因素。进一步对径向分布函数分析确定了NaY沸石中S—Na,CHsp2—Na之间存在独特的作用位。     

Comprehensive and Facile Synthesis of Some Functionalized Bis-Heterocyclic Compounds Containing a Thieno[2,3-b]thiophene Motif

A comprehensive and facile method for the synthesis of new functionalized bis-heterocyclic compounds containing a thieno[2,3-b]thiophene motif is described. The hitherto unknown bis-pyrazolothieno[2,3-b]thiophene derivatives 2a-c, bis-pyridazin othieno[2,3-b]thiophene derivatives 4, bis-pyridinothieno[2,3-b]thiophene derivatives 6a,b, and to an analogous bis-pyridinothieno[2,3-b]thiophene nitrile derivatives 7 are obtained. Additionally, the novel bis-pyradazinonothieno[2,3-b]thiophene derivatives 9, and nicotinic acid derivatives 10, 11 are obtained via bis-dienamide 8. The structures of all newly synthesized compounds have been elucidated by (1)H, (13)C NMR, GCMS, and IR spectrometry. These compounds represent a new class of sulfur and Nitrogen containing heterocycles that should also be of interest as new materials.